Process for the manufacture of synthesis gases



Nova 14, 1950 E. H. RElcHL 2,529,630

PROCESS FOR THE MNUFACTURE OF SYNTHESIS GASES Filed April 25. 1947 v 2 Sheets-fsheet 1 Cycle as /f dmaararr 7 Feed Invenor: Eric H. Reich! 9' BIV 'ww'aq'hu #Harney Non 14, 1950 E. H. RElcl-u.

PROCESS FOR THE HANUFACTURE OF SYNTHESIS GASES Filed .April 25. 194'? 2 Sheets-Sheet 2 Patented Nov. 14, 1950 PROCESS FOR THE MANUFACTURE F SYNTHESIS GASES Eric H. Reichl, Orinda, Calif., assigner to Stanolind Oil and Gas Company, Tulsa, Okla., a corporation oi Delaware Application April 25, 1947, Serial No. 743,889

1 Claim.

This invention relates to hydrocarbon synthesis and it pertains more particularly to an improved method and means for preparing a mixture of hydrogen and carbon monoxide for use as feed in the synthesis of hydrocarbons. More particularly it relates to an improved method and means for producing carbon monoxide and methane in controllable proportions.

This application is a continuation-in-part of my copending application S. N. 619,246, iiled September 28, 1945, now abandoned.

Systems have heretofore been proposed for the production of mixtures of hydrogen and carbon monoxide derived from natural gas, but the prior systems have a number of disadvantages among which is the fact that the proportions of hydrogen and carbon monoxide in the produced gas mixture could not be readily controlled when obtaining optimum converslon of methane. One prior art method is to endothermically convert a mixture of carbon dioxide, water and methane; another is to eliect partial combustion of methane with oxygen or water. The efliciency of a hydrocarbon synthesis make gas plant employing the partial combustion of methane to produce hydrogen and carbon monoxide is increased with increase in outlet temperature of the gases leaving the combustion chamber but in practice this outlet temperature is limited by the tendency of the hydrocarbons to form freecarbon.

It is, therefore, a primary object of this invention of provide method and means for minimizing carbon formation while at the same time permitting the use of optimum temperatures in the combustion zone. Another object of this invention is to provide an improved system for converting hydrocarbon gas, such as natural gas containing methane into normally liquid hydrocarbons. Another object of the invention is to provide a simplified and improved hydrocarbon synthesis employing natural gas as the raw material. Still another object is to provide a system adapted to produce hydrogen and carbon monoxide in selected and variable proportions. A further object ls to provide a system of increased carbon eilciency wherein residual gases from the hydrocarbon synthesis proper are converted into synthesis feed.. These and other objects of the invention will become apparent as the detailed description thereof proceeds.

Briefly, my invention comprises the preparation of synthesis gas in a multi-stage system. In the first stage recycle gas from a subsequent hydrocarbon synthesis and comprising carbon diox- \t`de and/or water vapor or recycle gas enriched with natural gas are preheated in the presence of catalyst. This is desirable because a much greater amount of heat can be absorbed than is possible in a simple heat exchanger for a given outlet temperature. The partially reformed and preheated products are then supplied to a combustion zone wherein oxygen is added and substantially complete conversion of the hydrocarbons is effected to produce a mixture of hydrogen and carbon monoxide. Since for mechanical reasons, there is a limit to the maximum temperature to which the gases entering the combustion zone can be preheated, the primary effect therefore of the greater absorption of heat in the rst stage is that a higher temperature is developed in the combustion zone. This higher temperature and the dilution elect of the recycle gases cooperate to minimize carbon formation.

The invention will be more clearly understood from the following detailed description read in conjunction with the accompanying drawings which form a part of the specification and wherein:

Figure 1 is a schematic ilow diagram illustrating one embodiment of the invention as applied to a hydrocarbon synthesis operation; and

Figure 2 is a diagrammatic showing of the details of a modified gas preparation unit according to this invention.

In these specific examples a system will be described for handling natural gas which consists essentially of methane, although diluent nitrogen may be present. The hydrocarbon feed introduced via line I 0 and a controlled amount of water vapor via line Il are commingled with recycle gas from line I2 and introduced into the furnace I3 at a pressure of about 190 pounds per square inch. The furnace I3 can be operated as a simple preheat zone in the absence of catalyst, wherein the recycle gas, water vapor and hydrocarbon feed are preheated to a temperature of about 1400 F. It should be pointed out that the temperature of this preheating operation ls limited by the mechanical strength and by the creeping stress of the available materials of construction. Therefore, in a preferred operation the furnace I3 can be provided with a reformer catalyst in the tubes IBA and in that event partial endothermic conversion of methane is eiiected at a temperature of between about 1200 and about 1500 F., for example at about 1400 F'., and under a pressure of about 190 pounds per square inch. Under these latter conditions between about 10 and about 45% of the methane is consumed by endothermic reactions in the preheat step to produce carbon monoxide and hydrogen.

A preferred reforming catalyst is a Group VIII metal, such as nickel or other metal oxide, which can be either unsupported or supported on clay, Kieselguhr, silica gel, alumina, Super Filtrol, and

` the like. In either erkent, the catalyst can be promoted by a metal or metal compound, for example, the oxide of aluminum, magnesium, cerium, uranium, chromium, molybdenum, vana dium, and the like.

Partially reacted and preheated gases from furnace I3 are supplied by line I8 to the combustion chamber Ii. These gases, preheated in accordance with this invention, now have a total heat content, in the form of sensible heat and heat derivable therefrom by combustion, greater than the identical gases preheated by the conventional indirect heat exchange method to the same temperature. As pointed out above, this brings about a higher temperature in the combustion zone I8.

Oxygen is supplied via line Il to the compressor I5 which may be in two or more stages and withdrawn from the compressor I5 at a temperature of about 300 F. and a pressure of about 200 pounds per square inch. This oxygen is then supplied via line I4 to the combustion chamber I6, but may in some instances be further pre'- heated to about 1000 F. before introduction into the combustion chamber IB. The preheated gases from furnace I3, on the other hand, enter the combustion chamber I6 via line I8 at a temperature of between about 1200 and 1500 F. and under a pressure of about 190 pounds per square inch. At the inlet of chamber Il a muiile can be provided to maintain a zone of substantially higher temperature of between about 2200 F. and 2400" F. In any event, the hot gases from the furnace I3 and oxygen from line Il are then thoroughly mixed within the combustion chamber Il where the conversion of methane with carbon dioxide, water vapor and oxygen is effected to produce a gaseous mixture of hydrogen and carbon monoxide, this gas mixture being hereinafter referred to as synthesis 'feed gas.

The space velocity through chamber I6 should be sufficient to give a contact time of between about 3 and about 30, for example of between about 5 and 10 seconds. The temperature of this operation is preferably at least about 2100 F.

and the outlet pressure may be as high as about Y 190 pounds per square inch, for example, about 185 pounds per square inch. Carbon formation is negligible under these conditions whereas it is a serious disability in the methods of the prior art wherein oxygen and methane are reacted even at somewhat lower reaction temperatures. This improvement is attributed to the combustion at the higher temperature developed due to the high degree of preheat and to the dilution of the methane with carbon monoxide and hydrogen prior to combustion with oxygen.

The synthesis feed gases withdrawn fromV the chamber IB at a temperature of about 2100 F. and a pressure of about 190 pounds per square inch are conducted via line II through a cooler or heat exchanger diagrammatically identified by the reference numeral 20. If desired the heat exchanger can be the furnace I3 as described in a second embodiment of this invention which is schematically illustrated in Figure 2. Thus the synthesis feed gas can be passed about the catalyst tubes I3a and withdrawn from the turbulent suspended phase.

Ytype or of the iron type.

4 chamber I 3 at a substantially reduced temperature. The temperature of the product gases in line 2| can be further cooled below about 600 F. and supplied to the synthesis reactor 23, together with recycle gas supplied via line 22.

The synthesis feed gas after preliminary cooling may be further cooled to about 550 F. or lower in an after-cooler (not shown) in line 2| and introduced into the synthesis reactor 23 together with recycle gas from line 32 where it is exothermically reacted in the presence of a nely divided catalyst maintained in a dense The catalyst for synthesis reaction can be either of the cobalt The cobalt type promotes the reaction:

2zHz+rCO (CHa) :rv-f-zHzO (1) and the iron type catalyst promotes the reaction:

3.1:Hz-l-3mCO-2 (CH2) z-l-:cHzO-l-:CO: (2)

In either case the catalyst should be in finely divided form so that it can be uidized by gases or vapors flowing upwardly through the catalyst at low velocity.

The temperature of the synthesis step when employing an iron type catalyst usually is within a range of between about 450 and about 675 F., for example, about 550 F. With a cobalt type catalyst the temperature of the synthesis step is usually within the range of about 225 and 450 F., for example, between about 325 and 395 F. in order to prevent the temperature level of the reactor from gradually increasing, i. e.. to remove the heat of exothermic reaction, a plurality of individually controlled bayonet-type cooling tubes 24 may be provided within the mass of turbulent catalyst. The details of the cooling system, however, do not form a part of this iniinvention and will not be described in further deall.

In systems of this type catalyst solids of small particle size are iluidized by upflowing gasiform materials within the reactor so that the catalyst within the reactor is maintained in a turbulent liquid-like dense phase. the 'extreme turbulence of the suspended catalyst particles serving to maintain substantially the entire mass of catalyst at a uniform temperature. The catalyst particles are of the order of 2 to 200 microns or larger, preferably 20 to 100 microns in particle size. With vertical gasiform uid velocities of the order of about 0.5 to 5, preferably between about 1 and 4. for example, about 2 feet per second, a liquid-like dense phase of catalyst is obtainedin which the bulk density is between about 30 and about 50 per cent, preferably between about 40 and about 80 per cent, e. g., about 60 per cent of the density of the settled catalyst material. 'Ihe vertical velocity of the gasiform fluids is in any event regulated so as to produce a turbulent suspension of catalyst within the reactor.

An active iron type catalyst can be prepared by a number of methods well known in the art, for example. by oxidizing iron in a stream of oxygen to produce a fused mass and then crushing the fused oxide. A very effective and economical catalyst can be prepared by iirst roasting iron pyrites. Another catalyst is one of the precipitated type which may be supported on Super Filtrol or other nely divided inert carriers. The iron catalyst. however derived, can be promoted by the addition of between about 0.5 and about 1.5% of a metal alkali compound such as by adsorbing KF thereon before condii tioning. The promoted iron catalyst is then treated with hydrogen before use in the synthesis of hydrocarbons.

A preferred technique for preparing catalyst is to roast a material containing a compound of iron with a combustible material or in admixture with a combustible material. Thelheat of combustion of the combustible components should be sumcient to raise the temperature during the roasting operation to at least 1500 F. Examples of suitable combustible components are sulfur and carbon.

An excellent method of catalyst preparation is to admix hematite (FezOn) with about 2% or more potassium carbonate. heat the mixture to a temperature above 1000 C.. i. e., to effect incipient fusing or sintering, and to convert the iron oxide to Fea04. extract excess potassium from the sintered mass with water so that only about l to 2%. e. g., about .5% potassium will remain. grind the catalyst to the desired particle size and reduce the FeaOs containing the residual potassium by treatment with hydrogen.

. The synthesis gas stream in line 2| is introduced into the reactor 23 at a low point therein preferably through a distributor plate. The reactor 28 comprises an elongated vessel having an enlarged upper section 28 wherein the catalyst settles out from the reaction products by reason of the reduced velocity therein resulting from increased cross section of the vessel and reduction in volume of the feed gases by reaction. The velocity reduction results from the reduction in volume of the reacting gases and from the increased cross sectional area of the reactor 28.

'I'he gasiform product in line 28 is cooled in heat exchanger 3| from a temperature of about 600"l F. to about 350 F. at a pressure of about 140 pounds per square inch. The cooled product is introduced into wax separator 40 which likewise is operated at a pressure of about 140 pounds per square inch. Hydrocarbon products boiling below about 350 F. at this pressure are removed from the separator 40 via line 4I. The products boiling above about 350 F. at 140 pounds per square inch are withdrawn from the separator 40 via line 42 and comprise essentially waxes.

The gasiform products in line 4I are further cooled in heat exchanger 43 to a temperature of aboutI to 100 F. below the boiling point of water at the partial pressure of water existing in the stream entering the condensen 'Ihe mol fraction of the water-in the eilluent stream 4I will be a function of the gas mixture used as feed, the conversion level, and the product distribution.A Ordinarily the mol fraction will be within the range of 0.1 to 0.5.

The cooled mixture is introduced into the water separator 44 and a substantially pure water fraction is removed via line 45. A portion of this water fraction can be used as a scrubber water as described hereinafter or it may be discarded as the net product water. A liquid hydrocarbon fraction is withdrawn from the intermediate separator 44 via line 46 and may comprise substantial amounts of oxygenated compounds.

The gases from gas separator 49 withdrawn via line 54 are introduced into knockout drum 55 preceding the compressors 51 and 58. 'This knockout drum 55 serves to remove residual condensable hydrocarbons and water as is desirable practice prior to compressing the gases.

The gas stream in line 56 which is removed from knockout drum 55 is split and the separate portions supplied to the compressors 81 and I8. About 50 mol per cent of the gas stream is raised in pressure to about 150 pounds by compressor 51 for internal recycle via line 22 to the hydrocarbon synthesis reactor 22. The remainder of the gas stream is raised in pressure to about 260 pounds per square inch, cooled in cooler 58 to a temperature oi' about 100 F. and introduced into the knockout drum BI via line 80. The liquid phase from the knockout drum 5I is withdrawn via line l2 and comprises predominantly water together with some oxygenated compounds and hydrocarbons. The gasiform phase from knockout drum 8| is introduced via line 63 into a water scrubber 64. scrubbing water is supplied via line 65 and may be derived from water separator 44 and line 45. An aqueous phase comprising oxygenated compounds is withdrawn Ifrom the water scrubber 84 via line 86 and may be processed as described in connection with the other water fractions including oxygenated compounds in line 52. The scrubbed reaction products comprising unreacted gases together with hydrocarbons prof duced in the synthesis are supplied via line 51 to the oil absorber 10.

The product gases inl line 81 are introduced into the oil absorber 10 and scrubbed with an absorber oil introduced at about 100 F. through line 'II forv the recovery of condensable hydrocarbons. In the oil absorption system a pressure of about 255 pounds per square inch is maintained and about 90 per cent recovery of net pentanes is attained from the rich absorber oil in line 12. The unabsorbed gases which leave the top of theabsorber 10 through line 86 can be processed for the recovery oi.' the useful hydrocarbons by absorption or the like and the residual gases recycled via line I2 to the reformer I3. In the illustrated embodiment the gases in line are introduced into acid absorber 81 which is supplied with acid by line 88. Rich acid is withdrawn by line 89 for recovery or conversion of the absorbed hydrocarbons as taught in my copending application SerialNo. 619,246.

Lean gases are removed overhead 'via line 90 and may be recycled via line I2 to furnace I 3 although a portion may be vented by line 9| to fuel to purge nitrogen from the system.

Referring to Figure 2, a recycle gas fraction including hydrogen, carbon dioxide, a minor proportion of carbon monoxide, water and normally gaseous hydrocarbons is preheated to a temperature of about 1000 F. and supplied via line II2 at about 300 pounds per square inch to an endothermic catalytic reforming zone I I3. Extraneous steam can be supplied byline I I I.

Catalyst of the type described in connection with Figure 1 is packed in vertically disposed tubes |I3a and hot gases are circulated around the tubes to supply the endothermic heat of reforming. The partially reformed gases are withdrawn from the reforming chamber II3 by line II8 at a temperature of about l500 F. and a pressure of 290 pounds per square inch. These product gases from chamber I I3 include increased proportions of carbon monoxide, decreased proportions of carbon dioxide, about the same proportion of hydrogen and a smaller proportion of gaseous hydrocarbons than were supplied to the" reformer H3 by line II2. The partially reformed gases in line I I8 are commingled with extraneous natural gas supplied by line I I0 at a temperature oi about 1100 F. and a pressure of about 290 pounds per square inch". This mixture of gases tween about 1900 and about 2600 F. with an outlet temperature of about 2200 F. in line ill. However, within zone III a higher temperature of between about 2200 F. and 2600 F. may be maintained. In this chamber, the oxygen reacts exothermically with a part of the hydrocarbon constituents and provides the heat necessary for the endothermic reaction of the residual hydrocarbons with water and/or carbon dioxide. In some instances it may be desirable to include within chamber H6 a contacting material such as a bed of porous ceramic material but ordinarily such is not the case. Likewise, a checker work muille or mantle may be provided at the inlet of chamber H6.

The combustion products which are withdrawn from the combustion chamber IIS by line lll comprise predominantly carbon monoxide and hydrogen with a substantial proportion of water. These hot gases are passed through the shell of reformer lll and are withdrawn therefrom at a temperature of about 1520 F. and a pressure of about 275 pounds per square inch by line I 2|. Alternatively. the reformer tubes Illa may be placed within the combustion chamber H6 for the indirect heat exchange with the combustion products.

'I'he product gases in line |2I may be heat exchanged in parallel with the oxygen in line H4, with the extraneous natural gas in line H0, and with the recycle gas in line I I2 by exchangers |20, I20a and I20b to effect the desired preheating thereof. The gaseous mixture then can be further cooled for example by a steam generator |22 on line I2l to permit removal of the product water and the dry gas being supplied to the hydro- ,carbon synthesis proper as described in connection with Figure 1. If desired, a portion of the steam produced in generator |22 can be charged to the reforming system via line I I l.

It is also contemplated that in another embodiment of the invention separate mixtures of carbon monoxide and hydrogen may be generated independently in the combustion chamber IIS and reformer Il) operated in parallel and these exothermic and endothermic zones H3 and IIB may.

be in indirect heat exchange. The products from such parallel combustion and reformer zones can be subsequently mixed selectively to obtain the desired ratio of hydrogen to carbon monoxide suitable for feed in the synthesis of hydrocarbons. About 80 per cent conversion of carbon monoxide per pass can be effected in the synthesis reactor and a portion of the gaseous reactor eilluent including unreacted feed can be recycled to the reactor before removal of carbon dioxide. Carbon dioxide can, however, be recovered from the reaction products and portions thereof recycled 8 to the parallel combustion chamber and/or to the reformer furnace. Additional carbon dioxide, together with unreacted feed gas and methane can be recovered from the synthol product beyond the fractionation step and can be recycled to the reformer.

From the above detailed description it will be apparent that the objects of this invention have been accomplished and that a vastly improved system for deriving mixtures of carbon monoxide and hydrogen from light hydrocarbons has been provided.

Although certain preferred embodiments of apparatus and operating conditions have been described to illustrate the invention, it should be understood that various other modifications and operating conditions will be suggested to those skilled in the art without departing from the scope of the invention. Accordingly. the details are not to be construed as limiting the invention and it is intended that the scope of the invention be defined by the appended claim.

What I claim is:

In a process for producing a mixture of carbon monoxide and hydrogen for effecting synthesis with a promoted iron catalyst, the improved method of operation which comprises mixing water vapor with carbon dioxide and methane to form a reformer gas charge, contacting said gas charge with a reforming catalyst in a reforming zone at a temperature in the range of about 1200 to 1500 F. under conditions for converting only about 10% to 45% of said methane endothermically to produce a hot gas mixture containing carbon oxides, hydrogen and unreacted methane, adding both oxygen and additional methane to said hot gas mixture and effecting further con- ERIC H. REICHL.

REFERENCES CITED The following references are of record in the ille of this patent:

UNITED STATES PATENTS Number Name Date 1,847,242 Guyer et al. Mar. 1, 1932 1,929,665 Wilcox Oct. 10. 1933 2,135,058 Spicer et al Nov. 1, 1938 2,324,172 Parkhurst July 13, 1943 2,347,682 Gunness May 2, 1944 2,381,696 Shapleigh Aug. 7, 1945 

